RELATIVE REACTIVITIES AND LINEAR FREE-ENERGY RELATIONSHIPS IN COMPETITIVE ADDITION OF SUBSTITUTED PHENYL RADICALS TO VINYL MONOMERS

Relative rate constants have been determined for the addition of phenyl and substituted phenyl radicals to styrene, methyl methacrylate, methyl acrylate, and methacrylonitrile, all relative to acrylonitrile. These data have been correlated with σ0 constants for substituents in the radical by an expression in which the slope (ρM - ρAN) corresponds to the difference in polar response. These and other findings are discussed in terms of theories regarding reactivity in radical addition reactions and, particularly, with respect to a general treatment of such data based on studies of polymer radicals. © 1969, American Chemical Society. All rights reserved.